CN105199060B - A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof - Google Patents

A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof Download PDF

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CN105199060B
CN105199060B CN201510666030.0A CN201510666030A CN105199060B CN 105199060 B CN105199060 B CN 105199060B CN 201510666030 A CN201510666030 A CN 201510666030A CN 105199060 B CN105199060 B CN 105199060B
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acid
methoxyl group
integer
active macromonomer
ultra high
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CN105199060A (en
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张小富
赵利华
仲璇
白淑英
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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Abstract

The invention discloses a kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof, ultra high early strength poly-carboxylic water reducer of the invention has cationic charge in the molecular structure, promotes cement water and changes to react, accelerate the strength development of maturing, has super hardening effect;Due to its unique both sexes structure and space steric effect so that it has unique cement granules dispersibility, and water-reducing rate is high, and resistance to soil is good.

Description

A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof
Technical field
The invention belongs to polycarboxylate water-reducer field, more particularly to a kind of ultra high early strength poly-carboxylic water reducer and its preparation side Method.
Background technology
In recent years, the research of concrete admixture has tended to develop towards high-performance, pollution-free direction with production, concrete Water reducer is that application surface is most wide in concrete admixture, the maximum one kind of usage amount., can in water reducer incorporation fresh concrete The flocculent structure of cement granules is destroyed, plays a part of disperse cement particles and hydrated cementitious particle, so as to discharge flocculation knot Free water in structure, increase the mobility of concrete mix.PCEs water reducers belong to anionic surfactant, mix water In slurry body, adsorb in the cement particle surface with cation, and be dissociated into hydrophilic and oleophilic function organic anion base Group.
Water reducer molecular skeleton is made up of main chain and more side chain.Contain more active group, and polarity on main chain Relatively strong, by these active groups, main chain " can be anchored " on cement particle surface, and side chain has hydrophily, Ke Yishen Exhibition in the liquid phase, so as to form larger three-dimensional adsorption structure in cement particle surface, produces space steric effect, so that water Mud particle is scattered and stably.Carboxylic acid ion makes the negative electrical charge on cement granules band produce Coulomb repulsion work between cement granules With, and disperse cement granules, contact of the increase cement granules with water, make the abundant aquation of cement.In the mistake of disperse cement particles Cheng Zhong, the Free water that agglomerate is included is discharged, workability is improved, reduces and mix water.
Polycarboxylate water-reducer (PCEs) with combed molecular structure generally by polyethoxy (PEO) side chain graft to it is cloudy from Formed on the main chain of son, PEO side chains produce space steric effect between the cement granules for being suspended in aqueous phase, by adjusting PCEs Molecular structure, different purposes can be reached, as slump retaining is good, water-reducing rate is high, and cohesiveness is good, and resistance to mud is good etc., in addition low Cost, it is pollution-free the advantages that, polycarboxylate water-reducer research turn into domestic and international concrete admixture research and development focus.
The primary raw material of poly carboxylic acid series water reducer has unsaturated acids, such as maleic anhydride, maleic acid and acrylic acid, metering system Alkenyl material, poly styrene sulfonate or the esters such as the polymerizable carboxylic acid such as acid, polyalkenyl hydrocarbon, ether, alcohol and acrylates, ester, Benzenediol, acrylamide etc., synthetic method generally have polymerisable monomer to be directly copolymerized, polymerize Post functionalization method, in-situ polymerization With grafting etc..
Polymerisable monomer is directly copolymerized:This synthetic method usually first prepares the side chain polymeric monomer with polymerization activity (being usually methoxy polyethylene glycol methacrylate-styrene polymer), then the monomer of certain match ratio is mixed, directly use Polymerisation in solution and finished product.This polymerization, technique is simple, but on condition that want the polymerizable polymeric monomer of synthesizing activity, and it is big single The performance of body directly determines and affected the performance of final products polycarboxylate water-reducer.
The surface-active macromonomer that China market is used to produce PCEs water reducers at present mainly has:
MPEG:Poly glycol monomethyl ether
VPEG:4- hydroxy butyl vinyl ether APEOs
APEG:Allyl alcohol polyethenoxy ether
HPEG:Isobutene alcohol APEO
TPEG:Isoamyl alcohol polyoxyethylene ether
APEG is bar-shaped rigid structure, high to cement adsorbance, and TPEG microstructures are star-shape polymers, have flexibility Segment microstructure is few to cement adsorbance.
APEG is the primary raw material of synthesizing polycarboxylic acid high-performance water reducing agent, and the PCEs water reducers of synthesis have dispersiveness Well, the advantages that volume is low, and water-reducing rate is high, adaptability is good;Shortcoming is inferior suitability, and Slump Time losing of Large is big.HPEG with TPEG is the water reducer of raw material production, and water-reducing rate is more or less the same, but summer uses, and slump retaining gap is larger, and cement adaptability is slightly Difference.Using the polycarboxylate water-reducer that TPEG is main material production, water-reducing rate is high, and slump retaining is good, strong to cement adaptability, production Process equipment is simple, and by polycarboxylate water-reducer, manufacturer favors.But complexity due to China's concrete raw material and various Property, especially when the soil content of sandstone is big, the slump-loss of concrete is big, the polycarboxylate water-reducer produced by TPEG, Because even intercalation occurs for PEG side chains and soil, make its resistance to mud poor, can not meet the requirement of concrete construction performance.
RCOO-With Ca2+Ionization forms complex compound, reduces the Ca in solution2+Concentration, delay Ca (OH)2Form knot Crystalline substance, the formation of C-H-S gels is reduced, has delayed the aquation of cement.
The content of the invention
The invention provides a kind of ultra high early strength poly-carboxylic water reducer, the water reducer has cation electrodeposition in the molecular structure Lotus, the water of cement can be promoted and changed to react, accelerate the strength development of maturing, there is super hardening effect, and due to it Unique both sexes structure and space steric effect so that it has unique cement granules dispersibility, and water-reducing rate is high, resistance to soil Property is good.
The technical solution adopted by the present invention is:A kind of ultra high early strength poly-carboxylic water reducer, the ultra high early strength poly-carboxylic water reducer Structural formula such as formula (1) shown in:
Wherein a is 1~80 integer, and b is 1~80 integer, and c is 1~50 integer;L is 1~50 integer;
A isR is H or CH3;
B is
C is
N is
R2、R3And R4It is respectively C alone1-3Alkyl;X is Cl, Br or I;M is 5~200 integer, n be 0~50 it is whole Number, z is 1~150 integer.
As the further improvement to above-mentioned technical proposal, the m is 10~180 integer, the n be 0~40 it is whole Number, the z are 1~120 integer, and the X is Cl.
As the further improvement to above-mentioned technical proposal, the m is 12~100 integer, and the n is 0~30 Integer, the z are 1~100 integer.
Present invention also offers the preparation method of described ultra high early strength poly-carboxylic water reducer, methods described includes following step Suddenly:
By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, One kind in VPEG and TPEG, ALS, water and molecular weight regulator mixing, is warming up to 85~95 DEG C, is added dropwise and triggers Agent, is incubated after being added dropwise, and is then cooled to 45~50 DEG C, adds sodium hydroxide solution regulation pH to 7.0-8.0, obtains super morning Strength poly-carboxylic water reducer;
The surface-active macromonomer is the compound shown in formula (2), and the structural formula of the compound shown in the formula (2) is as follows:
R2、R3And R4It is respectively C alone1-3Alkyl;X is Cl, Br or I;M is 5~200 integer;N is 0~50 integer;z For 1~150 integer.M is 5~200 integer, and n is 0~50 integer, and z is 1~150 integer.
As the further improvement to above-mentioned technical proposal, the m is 10~180 integer, the n be 0~40 it is whole Number, the z are 1~120 integer, and the X is Cl.
As the further improvement to above-mentioned technical proposal, the m is 12~100 integer, and the n is 0~30 Integer, the z are 1~100 integer.
As the further improvement to above-mentioned technical proposal, the methacrylic acid, acrylic acid, itaconic acid and maleic anhydride In one kind, one kind in APEG, HPEG, VPEG and TPEG, the mol ratio of surface-active macromonomer and ALS is methyl One kind in acrylic acid, acrylic acid, itaconic acid and maleic anhydride:One kind in APEG, HPEG, VPEG and TPEG:It is active big single Body:ALS=1~6.0:1.0:1.0~3.0:0.2~6.0.
As the further improvement to above-mentioned technical proposal, the molecular weight regulator is in sulfhydryl compound and isopropanol At least one, the dosage of the molecular weight regulator is the surface-active macromonomer, methacrylic acid, acrylic acid, itaconic acid and One kind in maleic anhydride, 0.005 of a kind of and total mole number of ALS in APEG, VPEG, HPEG and TPEG ~5%.
As the further improvement to above-mentioned technical proposal, the sulfhydryl compound is 3- mercaptopropionic acids, TGA, mercapto Base ethanol or sodium formaldehyde sulfoxylate.
As the further improvement to above-mentioned technical proposal, the time for adding of the initiator is 1~10h, the insulation Time is 1~12h.
As the further improvement to above-mentioned technical proposal, the initiator be hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate and One kind in the aqueous solution of benzoyl peroxide;The dosage of the initiator is the surface-active macromonomer, methacrylic acid, propylene One kind in acid, itaconic acid and maleic anhydride, one kind and acrylamide and 2- acryloyls in APEG, VPEG, HPEG and TPEG 0.05%~5% of a kind of total mole number in amine -2- methyl propane sulfonic acids.
As the further improvement to above-mentioned technical proposal, the surface-active macromonomer is prepared by following steps:
1) synthesis of methoxyl group hydroxyl PEG intermediates
Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen Propane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates;
Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin;The reaction equation of this step For:
2) synthesis of methoxyl group PEG reactive intermediates
Methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and the polymerization inhibitor of synthesis in step 1) are added into reactor, Stir, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid;The reaction equation of this step is:
3) synthesis of surface-active macromonomer
Quaternization reactant and polymerization inhibitor are added into reactor, is warming up to 10-80 DEG C, is slowly added dropwise in step 2) and closes Into methoxyl group PEG reactive intermediates quaternization reactant solution, after being added dropwise, under the conditions of 10-80 DEG C, continue to protect Temperature reaction 1-10h, produces the surface-active macromonomer;
The quaternization reactant is N (R2R3R4), wherein R2、R3And R4It is respectively C alone1-3Alkyl;This step it is anti- The equation is answered to be:
Wherein, R1For R2、R3And R4It is respectively C alone1-3Alkyl;X is Cl, Br or I;M is 5~200 integer;n For 0~50 integer;Z is 1~150 integer.
As the further improvement to above-mentioned technical proposal, the quaternization reactant is trimethylamine, triethylamine, 3 third Amine, N, N- dimethyl amines, N, N- diethyl methyl amines, N, N- dimethyl propylamines, N, N- diisopropyl methylamines or N, N- diisopropyl Base ethamine.
As the further improvement to above-mentioned technical proposal, in the step 1), methanol, oxirane or oxirane with The mixture of expoxy propane, the mol ratio of epoxyhalopropane are methanol:The mixing of oxirane or oxirane and expoxy propane Thing:Epoxyhalopropane=1:5~200:1~150.
As the further improvement to above-mentioned technical proposal, in the step 2), methoxyl group hydroxyl PEG intermediates and olefin(e) acid Mol ratio be 1:1.0~8.0.
As the further improvement to above-mentioned technical proposal, in the step 3), quaternization reactant and the methoxy The mol ratio of base PEG reactive intermediates is 0.2~2:1.
As the further improvement to above-mentioned technical proposal, the catalyst in the step 1) is sodium hydride or sodium;It is described Catalyst in step 2) is at least one of methanesulfonic acid and p-methyl benzenesulfonic acid;The polymerization inhibitor is for hydroquinones and to first At least one of ether phenol;The dosage of the polymerization inhibitor for the methoxyl group PEG reactive intermediate molal quantitys 0.002%~ 0.010%.
Present invention also offers application of the described ultra high early strength poly-carboxylic water reducer in concrete.
The ultra high early strength poly-carboxylic water reducer of the present invention can accelerate water and the change effect of cement, have super hardening effect.This hair Bright ultra high early strength poly-carboxylic water reducer has resistance to mud, protects the effect of collapsing in normal concrete, in pipe pile body concrete, Acted on super hardening, can be achieved pile tube singly exempt from and it is double exempt from technique, without adding any active mineral admixture.
Relative to prior art, beneficial effects of the present invention are:
The ultra high early strength poly-carboxylic water reducer of the present invention is further improving water reducer using surface-active macromonomer as Material synthesis While space steric effect, cation is introduced in the molecule, is accelerated cement water and is changed to react, there is super hardening effect, simultaneously Cation has good anti-mud, so as to improve the water-reducing rate of water reducer, resistance to mud and the adaptability to cement.Have to soil More preferable tolerance, even intercalation does not occur with soil.
Compared with common polycarboxylate water-reducer, identical volume, the water-reducing rate of ultra high early strength poly-carboxylic water reducer of the present invention improves 10-20%.
To the concrete (clay content 5%) of high clay content, compared with common polycarboxylate water-reducer, identical volume is of the invention The water-reducing rate of ultra high early strength poly-carboxylic water reducer improves 20-35%.
The cation of the ultra high early strength poly-carboxylic water reducer of the present invention can suppress the expansion of soil, so as to reduce soil to additional The absorption of agent.When product of the present invention is added in cement slurry, the anionic charge of main chain is adsorbed in positively charged cement Particle surface, and the positive charge of side chain end group is then adsorbed in negatively charged cement particle surface, disperse cement particles.Due to more Hydroxyl and water add the viscosity of cement slurry into hydrogen bond, improve the mobility and cohesiveness of concrete mix.
The ultra high early strength poly-carboxylic water reducer of the present invention can accelerate water and the change effect of cement, have super hardening effect.This hair Bright ultra high early strength poly-carboxylic water reducer has resistance to mud, protects the effect of collapsing in normal concrete, in pipe pile body concrete, Acted on super hardening, can be achieved pile tube singly exempt from and it is double exempt from technique, without adding any active mineral admixture.
Embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention It is described further.It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention, following reality NM specific experiment method in example is applied, is generally carried out according to normal experiment method.
Embodiment 1
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, be injected separately into 1.0mol methanol, 80mol oxirane, 20mol epoxychloropropane and 3g sodium hydrides, stir, react 8h at 80 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.9mol methoxyl group hydroxyl PEG intermediates, 7.2mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene Diphenol, stir, react 15h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 1.0mol trimethylamines and 0.01g hydroquinones are added into glass flask, is warming up to 75 DEG C, be slowly added dropwise containing Trimethylamine solution (wherein, moles the hundred of methoxyl group PEG reactive intermediates of 0.5mol steps 2) the methoxyl group reactive intermediate Divide specific concentration 5%), after being added dropwise, under the conditions of 75 DEG C, to continue insulation reaction 1.5h, producing the surface-active macromonomer.
Embodiment 2
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, 1mol methanol, 5mol oxirane, 1mol epoxychloropropane and 2g hydrogen are injected separately into Change sodium, stir, react 2h at 80 DEG C, produce reaction product methoxyl group hydroxy intermediate;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.8mol methoxyl groups hydroxy intermediate, 0.85mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 3h at 70 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 0.1mol triethylamines and 0.01g hydroquinones are added into glass flask, is warming up to 80 DEG C, be slowly added dropwise containing (wherein, methoxyl group PEG reactive intermediates rub the triethylamine solution of 0.5mol steps 2) methoxyl group PEG reactive intermediates Your percent concentration is 12%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 1h, it is big single to produce the activity Body.
Embodiment 3
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, be injected separately into 1mol methanol, 200mol oxirane, 150mol epoxychloropropane and 2g sodium, stir, react 10h at 150 DEG C, produce reaction product methoxyl group hydroxy intermediate;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 1.0mol methoxyl groups hydroxy intermediate, 8.0mol maleic anhydrides, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 10h at 170 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 1.5mol tripropyl amine (TPA)s and 0.01g hydroquinones are added into glass flask, 80 DEG C is warming up to, is slowly added dropwise and contains (wherein, methoxyl group PEG reactive intermediates rub the tripropyl amine (TPA) solution of 0.75mol steps 2) methoxyl group PEG reactive intermediates Your percent concentration is 10%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 6h, it is big single to produce the activity Body.
Embodiment 4
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, be injected separately into 1mol methanol, 175mol oxirane, 75mol epoxychloropropane and 2g sodium, stir, react 8h at 110 DEG C, produce reaction product methoxyl group hydroxy intermediate;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.7mol methoxyl groups hydroxy intermediate, 4.2mol methacrylic acids, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene Diphenol, stir, react 15h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 0.5molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, is warming up to 50 DEG C, slowly The N, N- dimethyl amine solution (wherein, methoxyl group PEG of the methoxyl group PEG reactive intermediates of the step 2) containing 0.5mol is added dropwise The Mole percent specific concentration of reactive intermediate is 15%), after being added dropwise, under the conditions of 50 DEG C, to continue insulation reaction 10h, i.e., Obtain the surface-active macromonomer.
Embodiment 5
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, be injected separately into 1mol methanol, 100mol oxirane, 80mol epoxychloropropane and 2g sodium hydrides, stir, react 8h at 120 DEG C, produce reaction product methoxyl group hydroxy intermediate;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.8mol methoxyl groups hydroxy intermediate, 4.0mol methacrylic acids, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene Diphenol, stir, react 9h at 100 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 0.2molN, N- dimethyl propylamines and 0.01g hydroquinones are added into glass flask, is warming up to 30 DEG C, slowly The N, N- dimethyl propylene amine aqueous solutions (wherein, methoxyl group PEG of the methoxyl group PEG reactive intermediates of the step 2) containing 0.7mol is added dropwise The Mole percent specific concentration of reactive intermediate is 15%), after being added dropwise, under the conditions of 30 DEG C, to continue insulation reaction 10h, i.e., Obtain the surface-active macromonomer.
Embodiment 6
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, 1.0mol methanol, 100mol oxirane and 50mol expoxy propane are injected separately into Mixture, 100mol epoxychloropropane and 4g sodium hydrides, stir, react 9h at 120 DEG C, produce in reaction product methoxyl group hydroxyl Mesosome;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.7mol methoxyl groups hydroxy intermediate, 3.5mol acrylic acid, 1g methanesulfonic acids and the 0.01g hydroquinones of rapid 1) middle synthesis, stirring, 12h is reacted at 120 DEG C, produces reaction product methoxyl group PEG reactive intermediates;
3) 0.35mol trimethylamines and 0.01g hydroquinones are added into glass flask, 50 DEG C is warming up to, is slowly added dropwise and contains There are trimethylamine solution (wherein, the methoxyl group PEG reactive intermediates of 0.6mol steps 2) methoxyl group PEG reactive intermediates Mole percent specific concentration produces the big list of the activity 5%), after being added dropwise, under the conditions of 50 DEG C, to continue insulation reaction 5h Body.
Embodiment 7
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, 1.0mol methanol, 90mol oxirane and 20mol expoxy propane are injected separately into Mixture, 75mol Epiiodohydrins and 2.5g sodium hydrides, stir, react 7h at 100 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.8mol methoxyl group hydroxyl PEG intermediates, 2.4mol itaconic acids, 1.5g methanesulfonic acids and the 0.01g of rapid 1) middle synthesis are to methyl ether benzene Phenol, stir, react 15h at 120 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 6.0mol triethylamines and 0.01g hydroquinones are added into glass flask, 80 DEG C is warming up to, is slowly added dropwise and contains (wherein, methoxyl group PEG reactive intermediates rub the triethylamine solution of 0.65mol steps 2) methoxyl group PEG reactive intermediates Your percent concentration is 12%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 1h, it is big single to produce the activity Body.
Embodiment 8
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, 0.8mol methanol, 80mol oxirane and 16mol expoxy propane are injected separately into Mixture, 24mol epoxychloropropane and 4g sodium hydrides, stir, react 10h at 90 DEG C, produce reaction product methoxyl group hydroxyl PEG Intermediate;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.6mol methoxyl group hydroxyl PEG intermediates, 1.8mol methacrylic acids, 4g methanesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 15h at 90 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 1.0mol tripropyl amine (TPA)s and 0.01g hydroquinones are added into glass flask, 10 DEG C is warming up to, is slowly added dropwise and contains (wherein, methoxyl group PEG reactive intermediates rub the tripropyl amine (TPA) solution of 0.5mol steps 2) methoxyl group PEG reactive intermediates Your percent concentration is 10%), after being added dropwise, under the conditions of 10 DEG C, to continue insulation reaction 10h, it is big single to produce the activity Body.
Embodiment 9
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, 0.5mol methanol, 60mol oxirane and 20mol expoxy propane are injected separately into Mixture, 2mol epoxy bromopropanes and 2g sodium hydrides, stir, react 9h at 90 DEG C, produce among reaction product methoxyl group hydroxyl Body;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.6mol methoxyl groups hydroxy intermediate, 2.4mol maleic anhydrides, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 3h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 0.12molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, is warming up to 80 DEG C, is delayed The slow N that the methoxyl group PEG reactive intermediates of the step 2) containing 0.6mol are added dropwise, N- dimethyl amine solution (wherein, methoxyl groups The Mole percent specific concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 3h, Produce the surface-active macromonomer.
Embodiment 10
One embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave of closing, it is injected separately into the mixed of 1mol methanol, 165mol oxirane and 35mol expoxy propane Compound, 120mol epoxy bromopropanes and 3g sodium hydrides, stir, react 10h at 130 DEG C, produce in reaction product methoxyl group hydroxyl Mesosome;
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.9mol methoxyl groups hydroxy intermediate, 1.3mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 20h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates;
3) 0.75molN, N- dimethyl propylamines and 0.01g hydroquinones are added into glass flask, is warming up to 50 DEG C, is delayed The slow N that the methoxyl group PEG reactive intermediates of the step 2) containing 0.72mol are added dropwise, N- dimethyl propylene amine aqueous solution (wherein, methoxyl groups The Mole percent specific concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 50 DEG C, to continue insulation reaction 5h, Produce the surface-active macromonomer.
Embodiment 11
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer described in 0.7mol embodiments 1,0.7mol acrylic acid, 0.7mol TPEG, 1.4molmol ALSs and 500ml deionized waters, the molecular weight regulator are 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is big for the activity Monomer, methacrylic acid, the 0.5% of ALS and TPEG total mole numbers, are warming up to 85 DEG C, the water-soluble of initiator are added dropwise Liquid, the initiator are the potassium peroxydisulfate that mass concentration is 10%, and the dosage of the initiator is the surface-active macromonomer, methyl 0.5%, time for adding 2h of acrylic acid, ALS and TPEG total mole numbers, after being added dropwise, insulation reaction 2h, It is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust pH=7.0, produce ultra high early strength poly-carboxylic water reducer.
Embodiment 12
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer described in 0.5mol embodiments 2,1.5mol itaconic acids, 0.5mol HPEG, 3.0mol ALSs and 600ml deionized waters, the molecular weight regulator are TGA, and the dosage of the molecular weight regulator is big single for the activity Body, itaconic acid, the 5% of ALS and HPEG total mole numbers, are warming up to 95 DEG C, the aqueous solution of initiator are added dropwise, described Initiator is the ammonium persulfate that mass concentration is 20%, and the dosage of the initiator is the surface-active macromonomer, itaconic acid, allyl The 5% of base sodium sulfonate and HPEG total mole numbers, time for adding 3h, after being added dropwise, insulation reaction 4h, it is cooled at 45 DEG C, The NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 13
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer, 1.0mol methacrylic acids, 0.17mol TPEG, 1.0mol ALSs described in 0.5mol embodiments 3 With 500ml deionized waters, the molecular weight regulator is mercaptoethanol, and the dosage of the molecular weight regulator is big for the activity Monomer, methacrylic acid, the 0.005% of ALS and TPEG total mole numbers, are warming up to 90 DEG C, the water of initiator are added dropwise Solution, the initiator are the benzoyl peroxide that mass concentration is 15%, and the dosage of the initiator is big single for the activity Body, methacrylic acid, 0.05%, time for adding 10h of ALS and TPEG total mole numbers, after being added dropwise, protect Temperature reaction 12h, is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjusts pH=7.5, produce super hardening and gather Carboxylic acid water reducer.
Embodiment 14
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer, 0.75mol methacrylic acids, 0.25molVPEG, 1.0mol ALS described in 0.5mol embodiments 4 With 400ml deionized waters, the molecular weight regulator is isopropanol, and the dosage of the molecular weight regulator is big single for the activity Body, methacrylic acid, the 5% of ALS and VPEG total mole numbers, are warming up to 85 DEG C, the aqueous solution of initiator are added dropwise, The initiator is the hydrogen peroxide that mass concentration is 10%, and the dosage of the initiator is the surface-active macromonomer, metering system 5%, time for adding 2h of acid, ALS and VPEG total mole numbers, after being added dropwise, insulation reaction 2h, are cooled to At 50 DEG C, the NaOH solution that mass concentration is 30% is added, pH=7.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 15
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer, 0.66mol maleic anhydrides, 0.33mol TPEG, 0.99mol ALSs described in 0.5mol embodiments 5 With 600ml deionized waters, the molecular weight regulator is sodium formaldehyde sulfoxylate, and the dosage of the molecular weight regulator is big single for the activity Body, maleic anhydride, the 1.2% of ALS and TPEG total mole numbers, are warming up to 95 DEG C, the aqueous solution of initiator are added dropwise, The initiator is the ammonium persulfate that mass concentration is 20%, and the dosage of the initiator is the surface-active macromonomer, maleic acid 2%, time for adding 3h of acid anhydride, ALS and TPEG total mole numbers, after being added dropwise, insulation reaction 4h, are cooled to At 45 DEG C, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 16
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer described in 0.5mol embodiments 6,1.2mol acrylic acid, 0.5mol APEG, 1.5mol ALSs and 500ml deionized waters, the molecular weight regulator are mercaptoethanol, and the dosage of the molecular weight regulator is big single for the activity Body, acrylic acid, the 0.25% of ALS and APEG total mole numbers, are warming up to 90 DEG C, the aqueous solution of initiator, institute are added dropwise It is the benzoyl peroxide that mass concentration is 15% to state initiator, and the dosage of the initiator is the surface-active macromonomer, propylene 0.1%, time for adding 6h of acid, ALS and APEG total mole numbers, after being added dropwise, insulation reaction 5h, cooling To at 50 DEG C, the NaOH solution that mass concentration is 30% is added, pH=7.5 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 17
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer described in 0.7mol embodiments 7,0.7mol maleic anhydrides, 0.35molAPEG, 0.7mol ALS and 400ml deionized waters, the molecular weight regulator are 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is big for the activity Monomer, maleic anhydride, the 2% of ALS and APEG total mole numbers, are warming up to 85 DEG C, the aqueous solution of initiator are added dropwise, The initiator is the potassium peroxydisulfate that mass concentration is 10%, and the dosage of the initiator is the surface-active macromonomer, maleic acid 1.5%, time for adding 2h of acid anhydride, ALS and APEG total mole numbers, after being added dropwise, insulation reaction 2h, cooling To at 50 DEG C, the NaOH solution that mass concentration is 30% is added, pH=7.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 18
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer described in 0.5mol embodiments 8,0.68mol acrylic acid, 0.17molHPEG, 1.0mol ALS and 600ml deionized waters, the molecular weight regulator are TGA, and the dosage of the molecular weight regulator is big single for the activity Body, acrylic acid, the 1.5% of ALS and HPEG total mole numbers, are warming up to 95 DEG C, the aqueous solution of initiator, institute are added dropwise It is the ammonium persulfate that mass concentration is 20% to state initiator, and the dosage of the initiator is the surface-active macromonomer, acrylic acid, alkene The 0.5% of propyl sulfonic acid sodium and HPEG total mole numbers, time for adding 7h, after being added dropwise, insulation reaction 4h, it is cooled to 45 DEG C Under, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 19
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer, 1.8mol acrylic acid, 0.6molTPEG, 2.4mol ALS and 500ml described in 0.6mol embodiments 9 Deionized water, the molecular weight regulator are mercaptoethanol, and the dosage of the molecular weight regulator is the surface-active macromonomer, third The 1.8% of olefin(e) acid, ALS and TPEG total mole numbers, is warming up to 90 DEG C, the aqueous solution of initiator, the initiation is added dropwise Agent is the benzoyl peroxide that mass concentration is 15%, and the dosage of the initiator is the surface-active macromonomer, acrylic acid, allyl The 4% of base sodium sulfonate and TPEG total mole numbers, time for adding 2.5h, after being added dropwise, insulation reaction 3h, it is cooled to 50 DEG C Under, the NaOH solution that mass concentration is 30% is added, pH=7.5 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 20
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer described in 0.7mol embodiments 10,1.75mol acrylic acid, 0.35mol HPEG, 1.2mol ALSs and 600ml deionized waters, the molecular weight regulator are TGA, and the dosage of the molecular weight regulator is big single for the activity Body, acrylic acid, the 1.5% of ALS and HPEG total mole numbers, are warming up to 95 DEG C, the aqueous solution of initiator, institute are added dropwise It is the ammonium persulfate that mass concentration is 20% to state initiator, and the dosage of the initiator is the surface-active macromonomer, acrylic acid, alkene The 5% of propyl sulfonic acid sodium and HPEG total mole numbers, time for adding 1h, after being added dropwise, insulation reaction 1h, it is cooled to 45 DEG C Under, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Application examples 1
The feasibility Experiment that super hardening carboxylic acid water reducer is applied in concrete
Concrete is prepared using the ultra high early strength poly-carboxylic water reducer synthesized in the embodiment of the present invention 11~20, gathered with common As a comparison, common polycarboxylate water-reducer is the polycarboxylate water-reducer without cation quaternary ammonium salt to carboxylic acid water reducer.Survey first Determine the water-reducing rate of the ultra high early strength poly-carboxylic water reducer and common polycarboxylate water-reducer synthesized in the embodiment of the present invention 11~20, Then concrete is prepared by following proportioning, determines the performances such as setting time, the maturing strength development of concrete.
The match ratio of normal concrete is as follows:
Cement:Flyash:Miberal powder:River sand:Rubble:Water:Common polycarboxylate water-reducer=200:90:60:800:1080: 165:8.5;
The match ratio of concrete is as follows made from the ultra high early strength poly-carboxylic water reducer of the embodiment of the present invention 11~20:
Cement:Flyash:Miberal powder:River sand:Rubble:Water:Polycarboxylate water-reducer=200 of the present invention:9:60:800:1080: 165:7.0.
Prepared by the ultra high early strength poly-carboxylic water reducer of the embodiment of the present invention 11~20 and common polycarboxylate water-reducer mixed Native effect is coagulated to be compared as follows:
As can be seen here, ultra high early strength poly-carboxylic water reducer of the invention is used in concrete, with common polycarboxylate water-reducer Compare, have more preferable dispersiveness to cement slurry, water-reducing rate improves, simultaneously because the cation of side chain is adsorbed with suppression to clay Make and use, resistance to mud well has super hardening effect simultaneously, cement hydrationization can be promoted to react, the strength development to maturing Play a driving role.
Application examples 2
Ultra high early strength poly-carboxylic water reducer is in double feasibility Experiments for exempting from the application of pile tube production technology
The selection of 1.1 raw material
(1) cement:From P II 52.5RPortland cement, specific surface area 320m2/kg。
The chemical composition (%) of the cement of table 2
SiO2 Al2O3 MgO CaO Fe2O3 Loss on ignition
23.82 3.37 4.85 61.20 4.32 2.44
(2) additive:From the ultra high early strength poly-carboxylic water reducer in embodiment 11~20.
The additive homogeneity index of table 3
Project Index Project Index
Outward appearance Crocus liquid Density (g/cm3) 1.017(25℃)
PH value 4.63 Chloride ion content (%) 0.01
Total alkali content (%) 0.18 Sodium sulphate content (%) 0.17
Solids content (%) 7.55
(3) sand:River sand, modulus of fineness 2.6, clay content 0.2%.
(4) rubble:5~25mm of granite, crush values index 8%, clay content 0.1%.
1.2 contents of the test and analysis
Under the conditions of natural curing, it is desirable to which concrete can reach 45- within 7-10 hours with form removal, concrete strength More than 50MPa, after the age of concrete is full 3~5 days, intensity can reach more than more than the 100% of design strength (80MPa), Meet PHC stake Standards.
1.2.1 the contrast test of ultra high early strength poly-carboxylic water reducer and naphthalene water reducer
1.2.1.1 the mix Design of table 4
Raw material Cement Sand Stone Additive Water
Dosage (kg/m3) 440 710 1320 10.12 110
Proportioning mixes raw material more than, and the raw material being stirred is fitted into mould, carries out prestressed stretch-draw, will Pile concrete after prestressed stretch-draw carries out low speed, low-medium speed, middling speed and high speed centrifugation, until pile tube is molded, with laggard Row demoulding natural curing, obtains PHC piles;It is respectively ultra high early strength poly-carboxylic water reducer and naphthalene to additive During based water reducer, under conditions of natural curing, the intensity of PHC pile tubes during different larval instar is tested, and test result is seen below Table.
1.2.1.2 the concrete strength of table 5 contrast (unit:MPa) volume is the same, and folding solid content is all 0.18%
As can be seen from Table 5, using ultra high early strength poly-carboxylic water reducer, concrete can realize early strong, natural curing 7-10h Its intensity reaches more than 43-52MPa, can safe form removal, when the age of concrete to 3-5 days, intensity reached design strength More than the 100% of (80MPa), meet PHC pile tube Standards, can dispatch from the factory safely.After dispatching from the factory, concrete strength is also continuing Increase, to 28 day age, concrete strength even can be close to C100.And using naphthalene water reducer, then intensity is formed slowly.
1.3 pairs are exempted from a maintenance processes
No longer need any fuel, the full temperature and humidity condition for leaning on the Nature, band mould natural curing in 7-10 hours, after form removal Timing water drenching in sand basin and autoclave, to ensure efficiently accomplishing for hydrated cementitious process early stage.Enter outdoor stockyard after 1 day, it is full It can be dispatched from the factory after 3-5 days.
1.4 pile tube performance comparisions
Using polycarboxylic admixture produce PHC pile tubes, amount of water significantly reduce (in the case where water reducer volume is constant, Folk prescription concrete water amount can reduce more than 15kg), on the premise of slump and workability is not changed, the ratio of mud It can control below 0.25, the remaining slurry poured out after tubular pile centrifugal is few, inner wall smooth and screed is relatively thin, is not easy soft slurry.By Reach the pile tube of 3-5 days to age and carry out core pulling experiment, it can be found that centrifugation layering unobvious, coarse-fine aggregate are evenly distributed, mixed The solidifying closely knit rare stomata of soil.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention And scope.

Claims (9)

  1. A kind of 1. ultra high early strength poly-carboxylic water reducer, it is characterised in that:The structural formula such as formula (1) of the ultra high early strength poly-carboxylic water reducer It is shown:
    Wherein a isInteger, b isInteger, c isInteger;L isInteger;
    A isR is H or CH3
    B is
    C is
    N is
    R2、R3And R4It is respectively C alone1-3Alkyl;X is Cl, Br or I;M isInteger, n is's Integer, z areInteger;
    The ultra high early strength poly-carboxylic water reducer is prepared with the following method:
    By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, VPEG and One kind in TPEG, ALS, water and molecular weight regulator mixing, is warming up to 85~95 DEG C, initiator is added dropwise, be added dropwise After be incubated, be then cooled to 45~50 DEG C, adjust pH to 7.0-8.0, obtain ultra high early strength poly-carboxylic water reducer;
    The surface-active macromonomer is the compound shown in formula (2), and the structural formula of the compound shown in the formula (2) is as follows:
    Wherein, R1For R2、R3And R4It is respectively C alone1-3Alkyl;X is Cl, Br or I;M isInteger, n ForInteger, z isInteger;
    The surface-active macromonomer is prepared by following steps:
    1) synthesis of methoxyl group hydroxyl PEG intermediates
    Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen third Alkane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates;
    Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin;
    2) synthesis of methoxyl group PEG reactive intermediates
    Methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and the polymerization inhibitor of synthesis in step 1) are added into reactor, is stirred, 3-15h is reacted at 70-170 DEG C, produces reaction product methoxyl group PEG reactive intermediates;
    Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid;
    3) synthesis of surface-active macromonomer
    Quaternization reactant and polymerization inhibitor are added into reactor, is warming up to 10-80 DEG C, synthesis in step 2) is slowly added dropwise The quaternization reactant solution of methoxyl group PEG reactive intermediates, after being added dropwise, under the conditions of 10-80 DEG C, it is anti-to continue insulation 1-10h is answered, produces the surface-active macromonomer;
    The quaternization reactant is N (R2R3R4), wherein R2、R3And R4It is respectively C alone1-3Alkyl.
  2. A kind of 2. preparation method of ultra high early strength poly-carboxylic water reducer as claimed in claim 1, it is characterised in that methods described bag Include following steps:
    By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, VPEG and One kind in TPEG, ALS, water and molecular weight regulator mixing, is warming up to 85~95 DEG C, initiator is added dropwise, be added dropwise After be incubated, be then cooled to 45~50 DEG C, adjust pH to 7.0-8.0, obtain ultra high early strength poly-carboxylic water reducer;
    The surface-active macromonomer is the compound shown in formula (2), and the structural formula of the compound shown in the formula (2) is as follows:
    R2、R3And R4It is respectively C alone1-3Alkyl;X is Cl, Br or I;M isInteger, n isInteger, z ForInteger;
    The surface-active macromonomer is prepared by following steps:
    1) synthesis of methoxyl group hydroxyl PEG intermediates
    Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen third Alkane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates;
    Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin;
    2) synthesis of methoxyl group PEG reactive intermediates
    Methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and the polymerization inhibitor of synthesis in step 1) are added into reactor, is stirred, 3-15h is reacted at 70-170 DEG C, produces reaction product methoxyl group PEG reactive intermediates;
    Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid;
    3) synthesis of surface-active macromonomer
    Quaternization reactant and polymerization inhibitor are added into reactor, is warming up to 10-80 DEG C, synthesis in step 2) is slowly added dropwise The quaternization reactant solution of methoxyl group PEG reactive intermediates, after being added dropwise, under the conditions of 10-80 DEG C, it is anti-to continue insulation 1-10h is answered, produces the surface-active macromonomer;
    The quaternization reactant is N (R2R3R4), wherein R2、R3And R4It is respectively C alone1-3Alkyl.
  3. 3. preparation method according to claim 2, it is characterised in that the methacrylic acid, acrylic acid, itaconic acid and horse The mol ratio of the one kind come in acid anhydrides, one kind in APEG, HPEG, VPEG and TPEG, surface-active macromonomer and ALS For one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride:One kind in APEG, HPEG, VPEG and TPEG:It is living Property polymeric monomer:ALS=1~6.0:1.0:1.0~3.0:0.2~6.0.
  4. 4. preparation method according to claim 2, it is characterised in that the molecular weight regulator is sulfhydryl compound and different At least one of propyl alcohol, the dosage of the molecular weight regulator are the surface-active macromonomer, methacrylic acid, acrylic acid, clothing One kind in health acid and maleic anhydride, a kind of and total mole number of ALS in APEG, VPEG, HPEG and TPEG 0.005~5%.
  5. 5. preparation method according to claim 2, it is characterised in that the time for adding of the initiator is 1~10h, institute It is 1~12h to state soaking time.
  6. 6. preparation method according to claim 2, it is characterised in that the initiator is hydrogen peroxide, potassium peroxydisulfate, over cure One kind in the aqueous solution of sour ammonium and benzoyl peroxide;The dosage of the initiator is the surface-active macromonomer, metering system One kind in acid, acrylic acid, itaconic acid and maleic anhydride, one kind and ALS in APEG, VPEG, HPEG and TPEG Total mole number 0.05%~5%.
  7. 7. preparation method as claimed in claim 2, it is characterised in that in the step 1), methanol, oxirane or epoxy second The mixture of alkane and expoxy propane, the mol ratio of epoxyhalopropane are methanol:Oxirane or oxirane and expoxy propane Mixture:Epoxyhalopropane=1:5~200:1~150.
  8. 8. preparation method as claimed in claim 2, it is characterised in that in the step 2), methoxyl group hydroxyl PEG intermediates with The mol ratio of olefin(e) acid is 1:1.0~8.0.
  9. 9. preparation method as claimed in claim 2, it is characterised in that in the step 3), quaternization reactant with it is described The mol ratio of methoxyl group PEG reactive intermediates is 0.2~2:1.
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Inventor after: Zhong Xuan

Inventor after: Bai Shuying

Inventor before: Zhang Xiaofu

Inventor before: Zhao Lihua

Inventor before: Bai Shuying

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